CN115819281B - Cyano-substituted p-phenylene ethylene derivative, preparation method and application - Google Patents
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- -1 Cyano-substituted p-phenylene ethylene Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims abstract description 5
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 6
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 5
- PNXWQTYSBFGIFD-UHFFFAOYSA-N 2-(4-iodophenyl)acetonitrile Chemical compound IC1=CC=C(CC#N)C=C1 PNXWQTYSBFGIFD-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000001376 precipitating effect Effects 0.000 claims 1
- 150000001875 compounds Chemical group 0.000 abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 10
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- 230000002776 aggregation Effects 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 6
- 238000010464 Blanc reaction Methods 0.000 abstract description 2
- 238000006000 Knoevenagel condensation reaction Methods 0.000 abstract description 2
- 238000005718 Kornblum oxidation reaction Methods 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 238000005755 formation reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 125000006617 triphenylamine group Chemical group 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical class N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003958 fumigation Methods 0.000 description 3
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- 239000003208 petroleum Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000009881 electrostatic interaction Effects 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a cyano-substituted p-phenylene ethylene derivative, a preparation method and application thereof, which are synthesized by Willamson ether formation reaction, blanc reaction, kornblum oxidation reaction, knoevenagel condensation and Suzuki-Miyaura coupling. The compound skeleton structure contains an electron-donating triphenylamine unit and an electron-withdrawing cyano unit, belongs to a typical D-A compound, and fluorescent tests of solutions with different polarities show that the compound shows obvious Intramolecular Charge Transfer (ICT) characteristic and aggregation-induced emission enhancement (AIEE) performance, and under the solid state condition, the compound obtains two crystalline states (R state and O state) with completely different fluorescence emission and stimulus response performances through simple solvent treatment. Wherein the O state is responsive to pressure, heat, and solvent vapor. The cyano-substituted p-phenylene ethylene derivative can be used for sensing, information storage, anti-counterfeiting ink and the like.
Description
Technical Field
The invention belongs to the field of photoelectric materials, and relates to a preparation method and application of cyano-substituted p-phenylene ethylene derivatives.
Background
Traditional fluorescent dye molecules (such as pyrene) have strong pi-pi interaction under solid state and aggregation condition due to a large plane conjugated system, so that the fluorescent dye molecules emit weak light or even do not emit light under the condition of concentrated solution and solid state, the phenomenon is called aggregation fluorescence quenching (Aggregation Cause Quenching, ACQ), most organic luminescent materials exist in a film shape or an aggregation state in practical application, and the ACQ phenomenon greatly limits the practical application of organic photoelectric materials. In 2002 Park SY et al reported that a cyano stilbene derivative also showed significant enhancement of fluorescence in solid and concentrated solutions, overcoming the problem of quenching of the aggregation state of conventional organic conjugated molecules. In addition, most of the cyano-stilbene frameworks with AIEE performance have complex intermolecular interactions under solid state conditions, such as pi-pi interactions, hydrogen bonds, electrostatic interactions, van der Waals forces and the like, and the weak non-covalent bond interactions are easily interfered by external stimulus, so that the molecular stacking mode is changed, and further the regulation and control of the molecular photoelectric performance are realized, so that the cyano-stilbene derivatives are widely applied to intelligent response materials. Such as sensing, information storage, anti-counterfeiting ink and the like
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a cyano-substituted p-phenylene ethylene derivative, a preparation method and application thereof, and the obtained cyano-substituted p-phenylene ethylene derivative has good fluorescence characteristic under the solid state condition and can respond to external stimulus.
In order to solve the technical problems, the invention adopts the following technical scheme:
cyano-substituted p-phenylene ethylene derivative with chemical structural formula of C 68 H 58 N 4 O 2 The molecular structure is shown as the following formula (1):
the preparation method of the cyano-substituted p-phenylene ethylene derivative comprises the following steps: compound 1 and triphenylamine 4-borate in tolene and H 2 The cyano-substituted p-phenylene ethylene derivative is formed by Suzuki-Miyaura coupling reaction in an O mixed solvent, and the structural formula of the compound 1 is as follows:
further, the molar ratio of the compound 1 to the triphenylamine 4-borate is 1:2.8, and the mixed solvent consists of tolene and H 2 O is formed by the volume ratio of 3:1; the coupling reaction was reacted under reflux for 24h. Preferably at 80℃for 24h.
Further, the preparation method of the compound 1 comprises the following steps:
(1) Reacting hydroquinone, bromobutane and potassium hydroxide in an organic solvent, cooling to room temperature after the reaction is finished, extracting, drying, leaching, filtering, concentrating in vacuum, and separating by column chromatography to obtain a compound 1a;
(2) Dissolving paraformaldehyde, hydrobromic acid and the compound 1a obtained in the step (1) in an organic solvent for reaction, cooling to room temperature after the reaction is finished, filtering, leaching, recrystallizing and drying to obtain the compound 1b.
(3) Dissolving the compound 1b and sodium bicarbonate in an organic solvent for reaction, cooling to room temperature after the reaction is finished, extracting, filtering, leaching, concentrating in vacuum, and separating by column chromatography to obtain the compound 1c.
(4) Compound 1c was reacted with p-iodobenzyl cyanide in THF/EtOH, and after the reaction was completed, the mixture was filtered. Eluting and drying to obtain the compound 1.
Further, the molar ratio of hydroquinone to bromobutane to potassium hydroxide in the step (1) is 1:2:3, the organic solvent in the step (1) is DMSO, the reaction temperature in the step (1) is 50 ℃, and the reaction time is 8 hours.
Further, the molar ratio of the compound 1a, the paraformaldehyde and the hydrobromic acid in the step (2) is 1:2:2, and the organic solvent in the step (2) is CH 3 COOH; the reaction temperature in the step (2) is 70 ℃ and the reaction time is 5h.
Further, the molar ratio of the compound 1b to sodium bicarbonate in the step (3) is 1:18.88, and the organic solvent in the step (3) is DMSO; the reaction temperature in the step (3) is 90 ℃ and the reaction time is 5h.
Further, the molar ratio of the compound 1c, the p-iodobenzyl cyanide and the sodium hydroxide in the step (4) is 1:2.2:2.4, and the organic solvent in the step (4) is THF/EtOH; the reaction temperature in the step (4) is room temperature, and the reaction time is 24 hours.
Further, the cyano-substituted p-phenylene ethylene derivative of the present invention was subjected to optical property measurement and thermal stability measurement. The cyano-substituted p-phenylene ethylene derivative is used for realizing encryption and identification of information by anti-counterfeiting ink.
The invention has the beneficial effects that: the invention discloses a preparation method and application of cyano-substituted p-phenylene ethylene derivative (CN-OPV), wherein the p-phenylene ethylene derivative is synthesized by Willamson ether formation reaction, blanc reaction, kornblum oxidation reaction, knoevenagel condensation and Suzuki-Miyaura coupling. The compound skeleton structure contains triphenylamine units for electron supply and cyano groups for electron absorption, belongs to a typical D-A compound, and fluorescent tests of solutions with different polarities show that the compound shows obvious Intramolecular Charge Transfer (ICT) characteristics.
In addition, the compound shows obvious aggregation-induced emission enhancement (AIEE) performance and better fluorescence property under aggregation conditions. Interestingly, under solid state conditions, the compound was treated with a simple solvent to give two crystalline states (R-state and O-state) with completely different fluorescence emission and stimulus response properties. Wherein the O state is responsive to pressure, heat, and solvent vapor. Based on the characteristics, the cyano-substituted p-phenylene ethylene derivative can be used for sensing, information storage, anti-counterfeiting ink and the like.
Drawings
FIG. 1 shows a compound 1 prepared in example 1 of the present invention 1 H NMR chart.
FIG. 2 is a block diagram of the present invention in example 2Cyano-substituted p-phenylethene derivatives of (a) 1 H NMR chart.
FIG. 3 is a photoluminescence spectrum of the cyano-substituted p-phenylene vinylene derivative prepared in example 2 according to the present invention under different conditions.
FIG. 4 is a graph showing the stimulus response of the cyano-substituted p-phenylenevinylene derivative produced in example 2 according to the present invention.
FIG. 5 is a schematic representation of the cyano-substituted p-phenylethene derivative of example 2 of the present invention as an anti-forgery ink for information storage.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
Example 1
The synthesis method of the compound 1 is as follows:
(1) Hydroquinone (4 g,36.33 mmol) and potassium hydroxide (6.12 g,108.98 mmol) were dissolved in DMSO. 1-Bromobutane (9.95 g,72.65 mmol) was added dropwise under nitrogen, heated at 50℃for 8h, quenched with water after the reaction was completed, cooled to room temperature and then quenched with CH 2 Cl 2 Extracting for three times, and using anhydrous Na for the organic layer 2 SO 4 Drying. Eluting, filtering, vacuum concentrating, and subjecting the crude product to column chromatography (silica gel; petroleum ether/CH) 2 Cl 2 V/v=6/1) to give compound 1a. The yield thereof was found to be 82%.
(2) In 1a (4 g,18 mmol), paraformaldehyde (2.71 g,90.36 mmol) and 20mL CH 3 HBr (10 mL,33% wt in CH) was slowly added to the COOH mixture 3 COOH) at 70 ℃ for 2h, adding water after the reaction is finished, filtering to obtain a white crude product, and subjecting the crude product to CHCl 3 /CH 3 OH was recrystallized to give compound 1b (10.98 g) in 68% yield.
(3) Compound 1b (4 g,9.85 mmol), naHCO 3 (15.62 g,185.99 mmol) was dissolved in 120ml DMSO, reacted at 90℃for 2h, cooled to room temperature, extracted with ethyl acetate and saturated NaCl solution, and the organic layer was taken up in anhydrous Na 2 SO 4 Drying, eluting, filtering, vacuum concentrating, and subjecting the crude product to column chromatography (silica gel; petroleum ether/CH) 2 Cl 2 V/v=6/1) to give yellow solid 1c (883 mg) in 40% yield.
(4) 2- (4-iodophenyl) acetonitrile (192.44 mg,0.79 mmol) and compound 1c (100 mg,0.36 mmol) in tetrahydrofuran/ethanol (40 mL, v/v=1:1) were added to a 100mL round bottom flask. NaOH (43.20 mg,1.08 mmol) was added. After stirring at room temperature for 24 hours, an orange precipitate formed. Collected by filtration, washed with water and ethanol, and dried under vacuum to give compound 1 (262 mg) as an orange solid. The yield thereof was found to be 83%. 1 H NMR(600MHz,CDCl 3 )δ8.02(s,2H),7.87(s,2H),7.80(d,J＝8.2Hz,4H),7.42(d,J＝8.2Hz,4H),4.12(t,J＝6.3Hz,4H),1.86–1.80(m,4H),1.56–1.51(m,J＝7.4Hz,4H),0.99(t,J＝7.4Hz,6H).
The reaction scheme is as follows:
example 2
Cyano-substituted p-phenylethene derivatives
In a 100mL Schlenk flask was added compound 1 (800 mg,1.10 mmol), triphenylamine 4-borate (890 mg,3.08 mmol), pd (PPh 3 ) 4 (12.06 mg,0.01 mmol) and Na 2 CO 3 (640 mg,6.04 mmol) and toluene/H were added under Ar atmosphere 2 O (64 ml, v/v=3:1). The reaction mixture was refluxed with stirring for 24h. After cooling to room temperature, CH is added to the mixture 2 Cl 2 (100 mL) extraction was performed three times. Anhydrous Na for organic layer 2 SO 4 Drying, leaching, filtering, vacuum concentrating, and adding petroleum ether/CH 2 Cl 2 (v/v=2/1) is used for eluting the mixture to obtain the red target product cyano-substituted p-phenylenevinylene derivative with 86 percent of yield.
1 H NMR(600MHz,CDCl 3 )δ8.07(s,2H),7.93(s,2H),7.75(d,J＝8.5Hz,4H),7.67(d,J＝8.5Hz,4H),7.52(d,J＝8.6Hz,4H),7.29(t,J＝7.9Hz,8H),7.17–7.14(m,12H),7.06(t,J＝7.4Hz,4H),4.16(t,J＝6.4Hz,4H),1.89–1.84(m,4H),1.59–1.52(m,4H),1.01(t,J＝7.4Hz,6H). 13 C NMR(151MHz,CDCl 3 )δ151.55,147.79,147.52,141.44,135.26,133.03,129.35,127.64,127.05,126.47,125.85,124.67,123.55,123.22,118.41,111.36,111.30,77.23,77.02,76.81,69.13,31.25,19.42,13.90,
Example 3
Photoluminescence spectra, quantum yield measurements
The optical properties of cyano-substituted p-phenylene ethylene derivatives were measured in different states and crystallized from DCM as shown in a in fig. 3 to give the red emission R state with the photoluminescence spectrum emission peak centered at 620 nm. Crystallization from toluene gives an orange emission O-state with emission peaks at 577nm and 594 nm. The absolute PL quantum yields of the cyano-substituted p-phenylene ethylene derivatives obtained by calculation of the O state and the R state by using an integrating sphere are respectively 0.62 and 0.21. The R state is fumigated by methylene dichloride to obtain an emitter very similar to the R state, and the emission center is 625nm. The O state shows stimulus response performance, is responsive to heating, grinding and DCM steam treatment, and can be used for anti-counterfeit ink for information encryption treatment.
Example 4
Stimulus response analysis
As shown in b of FIG. 4, the O-state sample was milled for 5 minutes, the fluorescence emission was changed from orange to orange-red, and the milled sample was subjected to fluorescence spectroscopy, and the emission peak was red-shifted from 594nm to 606nm, and the peak at 577nm was significantly reduced. And heating the O-state sample at 85 ℃ for 10 minutes, changing fluorescence emission into dark red, and obviously red-shifting a fluorescence emission peak, so that the fluorescence emission center of the heated sample is 640nm. And after the sample is heated and ground, the sample can return to orange emission after being fumigated by toluene. In addition, the O state also shows gas discoloration performance, and the DCM fumigation treatment is carried out for 2 minutes, so that an emitter very similar to the R state is obtained, and the emission center is 625nm.
The compound is used for preparing anti-counterfeiting ink in DCM and tolue suspension, as shown in a in fig. 5, the orange part of the four-leaf grass pattern is drawn by the tolue suspension, the red part is drawn by the DCM suspension, the orange part is changed into red (b in fig. 5, all are red) by heating or DCM fumigation treatment, and the orange emission can be recovered by toluene fumigation treatment after heating, so that the compound can be used for anti-counterfeiting ink for information encryption treatment.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. Cyano-substituted p-phenylene ethylene derivative with structural formula of C 68 H 58 N 4 O 2 The molecular structure is shown as the following formula (1):
formula (1).
2. The method for producing a cyano-substituted p-phenylene ethylene derivative according to claim 1, characterized by comprising the steps of: compound 1 and triphenylamine 4-borate in toluene and H 2 The cyano-substituted p-phenylene ethylene derivative is formed by Suzuki-Miyaura coupling reaction in a mixed solvent of O, and the structural formula of the compound 1 is as follows:
。
3. according to claimThe preparation method of the 2 cyano-substituted p-phenylene ethylene derivative is characterized by comprising the following steps: the molar ratio of the compound 1 to the triphenylamine 4-borate is 1:2.8, and the mixed solvent consists of toluene and H 2 O is formed by the volume ratio of 3:1; the coupling reaction was reacted at 80℃under reflux for 24h.
4. The method for producing a cyano-substituted p-phenylenevinylene derivative according to claim 2, characterized in that: the preparation method of the compound 1 comprises the following steps:
(1) Reacting hydroquinone, bromobutane and potassium hydroxide in an organic solvent, cooling to room temperature after the reaction is finished, and then extracting, leaching, filtering, drying and separating by column chromatography to obtain a compound 1a; the structural formula of compound 1a is as follows:
；
(2) Dissolving paraformaldehyde, hydrobromic acid and the compound 1a obtained in the step (1) in an organic solvent for reaction, cooling to room temperature after the reaction is finished, filtering, leaching, recrystallizing and drying to obtain a compound 1b;
the structural formula of compound 1b is as follows:
；
(3) Dissolving the compound 1b and sodium bicarbonate in an organic solvent for reaction, cooling to room temperature after the reaction is finished, extracting, leaching, precipitating the solvent, filtering, drying, and separating by column chromatography to obtain a compound 1c; the structural formula of compound 1c is as follows:
；
(4) And (3) dissolving the compound 1c and p-iodobenzyl cyanide and sodium hydroxide in an organic solvent for reaction, and filtering and leaching after the reaction is finished to obtain the compound 1.
5. The preparation of cyano-substituted p-phenylenevinylene derivatives according to claim 4, characterized in that: the molar ratio of hydroquinone to bromobutane to potassium hydroxide in the step (1) is 1:2:3, the organic solvent in the step (1) is DMSO, the reaction temperature in the step (1) is 50 ℃, and the reaction time is 8h.
6. The method for producing a cyano-substituted p-phenylenevinylene derivative according to claim 4, characterized in that: the molar ratio of the compound 1a, the paraformaldehyde and the hydrobromic acid in the step (2) is 1:2:2, and the organic solvent in the step (2) is CH 3 COOH; the reaction temperature in the step (2) is 70 ℃ and the reaction time is 5h.
7. The method for producing a cyano-substituted p-phenylenevinylene derivative according to claim 4, characterized in that: the molar ratio of the compound 1b to sodium bicarbonate in the step (3) is 1:18.88, and the organic solvent in the step (3) is DMSO; the reaction temperature in the step (3) is 90 ℃ and the reaction time is 5h.
8. The method for producing a cyano-substituted p-phenylenevinylene derivative according to claim 4, characterized in that: the molar ratio of the compound 1c to the p-iodobenzyl cyanide to the sodium hydroxide in the step (4) is 1:2.2:2.4, and the organic solvent in the step (4) is THF/EtOH; the reaction temperature in the step (4) is room temperature, and the reaction time is 24h.
9. Use of a cyano-substituted p-phenylenevinylene derivative according to claim 1 for anti-forgery ink in information storage.
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